Derek Nelson

Brett Michalk
Aziz Daabash
Amanda Mogollon

Introduction
Molecular Rotors
Catalyst
Nanofibers
Drug carriers
Questions

atc.atccu.chula.ac.th/research_matsci.htm&usg=__

What is a MOF?
Porous crystalline compounds forming 1,2 or 3
dimensional structures with the use of metal ions
Consist of a metal ion and a
an organic molecule, often
called a ligand.

atc.atccu.chula.ac.th/research_matsci.htm&usg=__

x6BkSuEgRdYhQHOQJpVldt61WLQ=&h=488&w =512&sz=34&hl=en&start=3&um=1&itbs=1&tbnid=34sU

9HfWW dTkfM:&tbnh=125&tbnw =131&prev=/images%3Fq%3DMetal%2Borganic%2Bframework%26um%3D1%26hl%3Den%26sa%3DX %26tbs%3Disch:1

http://www.cup.unimuenchen.de/ac/klausmb/mitarbeit/muellerbuschbaum/bilder/mof-bild1.gif

MOFs were born from

zeolites, porous crystalline
structures both found in
nature and man made
Zeolites are made from
aluminosilicate materials
Named from Greek when a
Swedish man observed water
boiling out of the rock
Used in Chem-E industry as
catalyst and adsobant

www.lenntech.com/images/zeolite3.jpg

MOFs are the next generation

Sigma-Aldrich, with BASF, have
developed a MOF with the surface
area of a football field in 1 gram

mf.mpg.de


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.com/data/X/8/MY424310/mortar-andpestleporcelain_10732033_25
0x250.jpg

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et.com/136-180/opplanetvwr-disposable-pelletmixers-and-cordlessmotor-v7338-901-0-5-mlpestle.gif

MOFs have been

synthesized in 2 ways

solvothermal techniques,
crystals are grown from a
hot solution of metal
precursor, such as a
metal nitrate solution
mechanochemical
methods, grinding, to
produce, however these
are none porous
mechanochemical
methods with the
addition of isonicotinate
(ISA) created porous 3D
crystals

http://www.cat-litter-critic.com/images/fresh-stepcat-litter.jpg

MOFs have limitless potential in many fields

Porous
MOFs large surface area to volume makes them
perfect to replace zeolites at every level when they
are available for mass production

Solid
As solid structures produced by mechochemical
synthesis, MOFs have very unique electrical
properties being explored

http://www.reflectscientific.com/im
ages/prod-graphitefabrication.jpg

Currently at the University of Colorado, Boulder

researchers are investigating the use of MOFs
to replace liquid crystals for optoelectronic
applications

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Rotating or twisting
molecules under an
electric field is the
principle behind liquid
crystals. MOF crystals
could lead to sturdier
materials to be used in the
data communications
industry
Currently tested MOFs do
not yet reach the barrier to
rotation to replace liquid
crystals

Structural and Catalytic Performance of a Polyoxometalate-Based

Metal-Organic Framework Having a Lanthanide Nanocage as a Secondary
Building Block
Dongbin Dang,, Yan Bai, Cheng He, Jian Wang, Chunying Duan,*, and Jingyang Niu

MOFs have characteristics that lend

themselves to being excellent
heterogeneous catalysts
Zeolites are currently holding the market for
acidic catalysts
MOFs require strong Lewis acid properties
in order to replace zeolites
for the cleaving of certain
compounds

http://www.chem.fsu.edu/~alabugin/Photos/dna_Cleavage_Cartoon.jpg

Strong Lewis acid

accepts a pair of electrons from another species

Used in the nano cleavage of different molecules

Polyoxometalates (POMs)

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/commons/6/6e/Dangclass8.png

Inorganic oxo clusters that contain transition

metals
Have many properties that can be used to
induce Lewis acid properties into MOFs

Heterogeneous Catalyst

For the purpose of this experiment hetero

catalyst has a higher conversion than homo
Properties used to see if experiment was a
success
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ses/facultypages/ukortz/image71_350x39
6.jpg

Compound {[Ho4(dpdo)8(H2O)16BW12O40]
3 2H2O}, compound 1, was thermally
crystallized from the solution
HoCl3 36H2O, 4,40-bipyridine-N,N0-dioxide
hydrate (dpdo),HoH2BW12O403 nH2O, and
hexahydropyrazine (pz)

Compound 1 crystallizes as shown below

Dongbin Dang,, Yan Bai, Cheng He

Synthesize a MOF with Lewis acid

properties, to create a very effective
heterogeneous catalyst.
Use the synthesized catalist to cleave a BNPP
molecule as shown
Use P NMR to monitor
the reaction kinetics

Dongbin Dang,, Yan Bai, Cheng He

Dongbin Dang,, Yan Bai, Cheng He

UV absorbance was used to determine if

the experiment was a success
The compound 1 MOF demonstrated
heterogeneous catalyst properties with a
high yield

Life cycle
How long will the catalyst last
Can it be regenerated?

Other MOFs
Can it be mechanochemically synthesized?
Are there more efficient compounds?

Inhar Imaz, Marta Rubio-Martnez, Wojciech J.

Saletra, David B. Amabilino, and Daniel
Maspoch

Creation of 1-dimensional infinite

coordination polymer particles (ICPs) via
conventional coordination chemistry
ICPs offer

Promising functionalities

Magnetism
Porosity
Ion exchange
Optical properties

Encapsulating matricies

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Martin et al. (2004)

First discrete metal-organic nanotubes by layer-by-layer growth.

Lin et al.

Created Gd(III) based nanorods used as contrast agents by

water-in-oil microemulsion based technique

Oh et al.

Porous In(III) based hexagonal nanorods by hydrothermal

synthesis

You and Lohs research groups

Creation of coordination polymer based gels and nanofibers.

Efficient in light harvesting due to 1-D structure.

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Purpose: Formation of long chiral coordination polymer

nanofibers
Conditions:

Ambient conditions
Use of aqueous/organic interfacial coordinative polymerization

Technique based on previous work involving Aspartic

acid reacted with transition metal ions to create
biorelated coordination polymers.

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta Rubio-Martnez

1) Aspartic acid and NaOH dissolved in EtOH/H2O mixture

(5:1)
2) Cu(NO3)2*6H2O dissolved in water.
3) Careful transference of both mixtures to a test tube.
4) After 3 days, fibers form at the interface of the layers.
5) During the next 2 weeks, the ethanol layer diffuses
into the aqueous phase, and causes formation of the
fibers oriented along the direction of diffusion.

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta Rubio-Martnez

Photomicrograph image of
fiber bundles shows:
Length
High orientation

Transmission electron
microscopy (TEM) depicts
Homogeneity of fibers
Diameter

Field-emission scanning
electron microscopy (FESEM)
confirms the uniformity of the
sample as well as the narrow
diameter distribution.

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta RubioMartnez

Confirmation of 1-D structure

Proposed formula [Cu(Asp)

(H2O)x]n
Energy dispersive x-ray confirmed
presence of copper, oxygen,
nitrogen, and carbon
IR spectra showed bands at
wavelengths that suggest the
presence of carboxylate groups of
aspartic acid functional groups, and
they are coordinating to the Cu(II)
ions.
Elemental analysis confirms 1:1
ratio of Cu(II) ions and Aspartic acid

http://en.wikipedia.org/wiki/File:L-aspartic-acid-3D-balls.png

When the aqueous and organic layers are

mixed after addition to the test tube, an
opaque blue gel is created.
Upon further examination (FESEM) it is
observed that the gel is made up of
homogeneous short-length nanofibers.
This result indicates that the length of the
nanofibers is dependent on the method of
synthesis.

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta RubioMartnez

Long chiral nanofibers can be

grown using traditional
coordination chemistry and
biologically derived components by
utilizing diffusion controlled growth
procedures.
Simple changes in the
experimental procedure can have
large effects on the end product
(nanofiber length and orientation)
Highly flexible composition of
coordination polymers can have a
huge impact on future applications.
http://www.mpip-mainz.mpg.de/groups/landfester/projects/dc_sem_fig1

Rachel C Huxford, Joseph Della Rocca and

Wenbin Lin

Metal-organic frameworks
(MOFs) present a new way to
introduce drugs to the body.
Offer high drug loadings,
biodegradability, and
versatile functionality.
Reduction to nano-scale will
increase viability of MOFs to
act as drug delivery vehicles.
http://www.dcfe.unimi.it/sezion3.jpg

Lots of progress in the

understanding of diseases,
but not nearly as much
progress in the treatment of
those diseases.
MOFs can help to target
specific distribution areas
(tumors for example) and will:
Lower the required doses
Extend the time the medication
is in the body
Optimize pharmacokinetics
Reduce side-effects

http://img.thebody.com/legacyAssets/08/76/cover.jpg

Important properties for MOFs used as drug

transporters:

Size
Drug loading
Surface properties
Drug release kinetics
Improved pharmacokinetics
Biocompatibility
Tissue specificity
Multiple agent engineering

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Major goal is to design a

carrier that both the ligand
and transition metal used
exhibit little toxicity to the
human body.
Iron, copper, manganese,
nickel, and zinc are all found
in the human body, however
little is known about possible
biological downfalls to each
of these metals.

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Materials of Institut Lavoisier (MIL)

Trivalent metal centers with carboxylic
bridging ligands
Large pores (25-34 )
Large surface area (3100-5900 m2/g)
Functional group incorporation
Two MOFs studied, MIL-100 and MIL101

Metalorganic frameworks as potential drug carriers

Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Both MIL-100 and MIL-101 are chromium based and are

tested with the storage and release of ibuprofen.
Drug loading
MIL-100 0.347g ibuprofen/g MOF
MIL-101 1.376g ibuprofen/g MOF
Difference attributed to pore size of MIL-101 at 12700 and
20600 (8200 and 12700 for MIL-100)

Drug release

Tested using simulated body fluid at 37 C

MIL-100 Initial release within two hours with full release after
three days
MIL-101 Steady release for eight hours with full release after
six days

http://www.itg.uiuc.edu/technology/reconstruction/scaffold-cells.jpg

The chromium used is highly

toxic in the human body, so an
iron analog, MIL-101(Fe) should
be used as a more suitable
drug carrier.
MIL-53 is another MOF in the
MIL family that has properties
that make it desirable for long
release (3 weeks) medications.
MIL family has the highest drug
loading capabilities of any
material previously studied.
http://struktur.kemi.dtu.dk/kenny/MIL_53_b.JPG

MIL family have hydrophobic pores, but what

about MOFs that use hydrophilic pores?
The hydrophilic pores will hold a positive or
negative charge, and the drug used will
contain opposite charges to the MOFs.
The Rosi group created a MOF consisting of
zinc(II) ions, adenine, and para-biphenyldicarboxylic acid.
This MOF can be cationically triggered to
release the drug contained inside.

Storage
0.22 g drug/g MOF
Loaded with a hydrochloride salt of procainamide

Release
Previously this drug is generally limited by its
rapid exit from the body, and requires re-dosing
every three to four hours
Use of MOF extended release time to 72 hours.

Metalorganic frameworks as potential drug carriers

Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Gaseous therapeutic
carriers Nitric Oxide

Antibacterial
Antithrombotic
Wound healing applications

MOF made from cobalt or

nickel and 2,5dihydroxyterephthalic acid.
Can absorb seven times
amount of NO as any other
MOF
Has little background release

Metalorganic frameworks as potential drug carriers

Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

NO loaded MOF tested on pig coronary

arteries induced vessel relaxation
Nickel and Cobalt are too toxic for biological
applications, but this work shows the ability
of MOFs to carry and release gaseous cargo.

http://pubs.acs.org/cen/img/83/i34/8334cov1aopening.gif

Previously discussed
MOFs cannot work
because of large size.
A reduction to the nano
scale (nMOFs) will allow
systemic circulation
through the body while
retaining the properties of
bulk MOFs
Big Picture:
Pharmacokinetic
improvements!
http://www.sciencedaily.com/images/2007/06/070627084654-large.jpg

Lin group fabricated nMOF designated NCP-1

Tb3+ ions and disuccinatocisplatin (DSCP)

~58.3 nm in diameter
Encapsulated in silica to enhance stability
Functionalized with c(RGDfk) to target an integrin over
expressed in many cancers

Once the MOF reaches the cancer cell, the drug is

reduced to a more toxic form to kill the cancer cell.

Metalorganic frameworks as potential drug carriers

Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Lin group also loaded a nano form of

MIL-101 with a cancer prodrug and
imaging agent.
Addition of imaging agent suggests
possible future of real time monitoring of
the therapeutic response to the drug.

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Drug carriers can be formed from a vast amount of

metal centers and connecting ligands to find desirable
characteristics for the specific application.
Many different drugs can be incorporated into the
MOF.
Therapeutic drugs in conjunction with imaging agents
offer new ways to study the real time effects of
medications.

Metalorganic frameworks as potential drug carriers

Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Investigate the toxic effects of metals

already found in the body for use in nMOFs
Explore additional slow release mechanisms
for prolonged exposure to the drug.
Design nMOFs for large surface area/volume
ratio to maximize drug loading capabilities.
Research coatings that will increase the
stability of the nMOFs and possibly help
contain the drug inside until the desired
location is reached.

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Rebuttal Group from U4

Oral Presentation and Slides

We agree that their should have been an introduction
slide, instead of just assuming the audience realized the
entire front matter before the three papers were the
introduction.
We agree that the Catalyst Paper slide title was
inappropriate and should have matched the other two
papers by using the title of the paper for the title of the
slided.
We agree that we should have stuck on one naming
convention for metal organic frameworks, either saying
its full description the whole time, or by condensing it to
MOF every time after defining it in the introduction. We
apologize for any distraction that this may have caused.
We agree that some slides should have contained larger
pictures, but for the most part we think that we filled the
slides in nicely with ample text/figures.

Technical
We agree that our introduction was lacking in technical
information to provide the audience with a complete
background for the papers.
We also agree that in the first paper the
heterogeneous/homogeneous catalyst properties
should have been better explained.
We agree the second paper was very well structured
and presented, however we also agree that we should
have done more to explain how this research will
further research in the field.
The third paper was not very descriptive on how the
drugs target certain areas of the body. We should have
done more in depth research to inform the audience
that the ligand can be an amino acid that helps the
MOF move to a targeted area.
Overall we agree that we should have had a technical
summary and additional research and benefits of our
presentation

U1 review of U4
Metal Organic Framework
Definition;
consisting of metal ions or
clusters coordinated to often
rigid organic molecules to form
one-, two-, or threedimensional structures that can
be porous

Importance;
Have potential to replace
zeolite
Have unique electrical
properties that will be very
useful in future electronics and
computing

http://medgadget.com/archives/2008/02/orga
nic_metal_hybrids_promise_materials_of_the_
future.html

About the presentation

Overall presentation
Well presented, well organized, clear slides
and great research work. Thank you for
the superb presentation.

Time length
It was little off the time limit of 30 minutes
but it wasnt a boring presentation. They
did well to engage the audiences and it
was a very good stuff to learn

Food
Provided (thank you)

Impact
We have an opportunity about the MOF
and about the research going on this topic
It is very helpful for some of us who is
considering nano-research as their career

Final thoughts
Such presentation will help in developing
the research and presentation skills for
undergraduate students like us.

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ights/Images/APS_SCIENCE_2008072
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Review of Group U4s Presentation-

By Group U2:
-Kyle Demel
-Keaton Hamm
-Bryan Holekamp
-Rachael Houk

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The presenters did really well at:

Food This group by far brought the best food to class. Ice cream

sandwiches, cookies, cupcakes how could we not give you an A

just for that?
Figures The graphics used throughout the presentation were

pertinent to the topics being presented. The use of graphics was very
important to help demonstrate the material being discussed. The
group did a good job of incorporating graphics onto every slide.
Structure The group followed a clear presentation and structure

order. They provided an outline and stuck with it. The outline could
have been done better. The topics in the outline were vague and did
not properly summarize each section.
Articles The presenters chose appropriate articles for this

presentation. A total of three articles were used. This is very

impressive considering that most groups chose to only report on one
pertinent article during their presentation. The speakers discussed
metal organic frameworks with respect to
catalysts (very important considering the reaction engineering
that many students have learned), amino
http://pubs.acs.org/cen/images/8003/8003notw1sphere.gif
acid nanofibers
(incorporating biology

The group could improve at:

Timing The group needs to do a better job coordinating the speaking

parts and for how long each group member will talk. Only two of the
group members presented, which is fine, but of these two members,
one spoke for five minutes, and the other spoke for twenty-five
minutes. That is clearly malproportioned. The speakers should
practice together ahead of time to smooth out transitions and even
out the amount of speaking parts.
Background The background was very brief, and predictably, not

very informative. The speakers rushed through the introduction in

about two or three minutes. More time should be committed to
communicating the basic material.
Slide Format The group clearly went with a template formatting and

meshed all the sections together. This led to striking inconsistencies

in formatting. The text and heading size varied between the slides.
Most slides also had too many words on them. These should be short
bullet points, not paragraphs! The figures also need to be bigger.
There is too much blank space on the slides. Space the text out more
if you have to, but do not leave half a slide blank without reason.
Stronger Beginning & End The opening was kind of weak; the
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Undergrad 2nd Review for Group

U4
Metal Organic Frameworks
Group U3:
Krista Melish
Kancewick
Phillip Keller

James
Mike Jones

Presentation Review: Ugrad

#4
Presentation Review
Introduction

Paper 2: Amino acid based metal organic

nanofibers

The introduction contained good

Effective introduction to the topic, and especially

information to describe what MOFs are, but

we would have liked to see more
information on their history.
The papers covered after the introduction
should have been mentioned even if each
paper has its own intro slides. This would
help the audience to see where the
presentation is going.
Paper 1: Catalyst
Intro slide communicated all necessary

information to understand the problem and

experiemnt.
The theory slide could have been more
effective. The last bullet about
heterogenous catalystdoesnt seem to be
correctly integrated. Heterogenous
catalysts simply are ones that have reaction
sites within them. Zeolites and MOFs are
both heterogenous catalyst types.
Explanation of the mechanism of using
polyoxometalates to obtain the desired
behavior in the MOF could have been done
better.

liked the history which put it in perspective.

The experiemnt and results where both explained

well, and in a way that was easy to understand.

The only thing that should have been better

clarified are the specific positive properties this

ICP yielded. The intro mentioned some areas
where the might ne useful, but there wasnt
much on how this experiment might affect future
things. It seemed like it didnt have an end goal
in mind in advancing the field.

Paper 3: MOFs as potential drug carriers

It is not apparent how MOFs can help target
specific distribution areas in the body as
mentioned in the intro. The rest of the
information is correct, but MOFs cant distinguish
between different areas of the body.
Good job explaining how high surface area of
MOF can lend istelf to storage and release of
medications, as well as why this fact is important.
Experimental results were presented in an easy
to understand way. The point was clear, and the
limtations of the mofs due to their toxicity was
also clearly presented. Would have liked a slide
on the specific methods used to create the MOFs.

Review Of Group U4 by

Group U5

Oral skills and preparation

very good.
First speakers seemed to
have practiced and knew
their information but later
speakers needed more work.
Great slide quality and
sequence. A lot of pictures,
figures, and graphics that
were helpful for
understanding

http://www.rsc.org/images/b808104b350-FOR-TRIDION_tcm18-128604.jpg

 Very good introduction.

Liked how they

described what MOFs
were, but would have
liked to learn more
about their history and
past work more.
Choice of papers were
relevant and interesting
Did not like how they
nicknamed the first
paper Catalyst Paper.
Would have preferred
for them to use the
actual title of the paper

Dongbin Dang,, Yan Bai, Cheng He

Dongbin Dang,, Yan Bai, Cheng He

 Jaynesh Shah
Greg Pudewell
Edwin L. Youmsi Pete
John Pack

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84654-large.jpg

 Both speakers were loud,

clear, audible and

maintained eye-contact
They were confident and
sounded knowledgeable
on the subject
The slides were visually
appealing and consistent
All the graphics in the
slides were appropriately
cited and were relevant
to the topic

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Speakers made good

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use of technical
jargon
The papers
discussed were
relevant and
interesting
Could and should
have discussed
further research a
little bit more

Metal Organic
Framework
Presented by: Group U4
Critiqued by: Group U6
Pavitra Timbalia + Michael
Trevathan

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Critique: Oral Presentation &

Slides
Slide Background made the font easy to read and the pictures

easy to see
The Overview slide did a good job summarizing the topics
ahead
Should have had a slide which said Introduction
http://www.how-tostudy.com/images/o Instead of saying Catalyst Paper could have just placed paper
ther-helpfularticles/making-antitle
oral-presentationspeaking.gif
The group did a good job in having graphics on each of the
slides however, one or two slides did not have any graphics
All of the graphics were referenced good job

We did not like the way the slides end maybe need an overall

conclusion slide to tie things together

The group presented well the other two members presented
for this presentation
Both presenters kept good eye contact with the
audience and good posture (Both were also dressed in business
clothes)
The first speaker spoke too fast more practice could have
helped him pace his talk better instead of making the
presentation look rushed
The second speaker was very thorough in his analysis of the two
papers and did a good job in explaining the research
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Critique Technical Content

Introduction was a bit rushed because of pace of speaker
It was, however, concise and gave a good overview of metal

organic frameworks
Choice of research papers seemed relevant to topic discussed
Three papers discussed which gave a good range of information on
current research
The second and third papers were more in-depth with the analysis
The paper on drug carriers was the most interesting since to us
http://www.medgadget.com/
archives/img/54747por.jpg
the research could assist advanced in the medical field
Each of the papers covered recent research in the field
The motivation for each paper given at the beginning something we really liked
Further research was incorporated at the end of the slides for
each paper would have liked to see the impact of this
research in the future
Like we said before, the presentation ended abruptly would
have liked to see a conclusions/summary slide or an overall
further research slide
We feel that there should have been a Works Cited slide to
let the audience know which references were used they were
not all cited well in the presentation
http://www.bioinfo.mpg.de/euclis/General/images/clockReferences.jpg

Review for U4
Jung Hwan Woo

 Overall, the presentation and the slides

were great.
The presentation contained several
different applications. It was a good
approach as it could introduce more
applications of MOFs to the audience.
However, this approach resulted in the
lack of depth in some of the research
topics introduced.
Some of the slides were a bit crowded
with text but it was ok.
I liked the option 1, option 2, etc.
approach.